TWI751983B - Adhesive composition and hot melt adhesive - Google Patents

Adhesive composition and hot melt adhesive Download PDF

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TWI751983B
TWI751983B TW105133478A TW105133478A TWI751983B TW I751983 B TWI751983 B TW I751983B TW 105133478 A TW105133478 A TW 105133478A TW 105133478 A TW105133478 A TW 105133478A TW I751983 B TWI751983 B TW I751983B
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acid
polypropylene
melting point
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TW105133478A
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TW201728724A (en
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橫道卓也
柏原健二
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日商東洋紡股份有限公司
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    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J123/00—Adhesives based on homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Adhesives based on derivatives of such polymers
    • C09J123/02—Adhesives based on homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Adhesives based on derivatives of such polymers not modified by chemical after-treatment
    • C09J123/10—Homopolymers or copolymers of propene
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J123/00—Adhesives based on homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Adhesives based on derivatives of such polymers
    • C09J123/02—Adhesives based on homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Adhesives based on derivatives of such polymers not modified by chemical after-treatment
    • C09J123/10—Homopolymers or copolymers of propene
    • C09J123/12—Polypropene
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/32—Layered products comprising a layer of synthetic resin comprising polyolefins
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B7/00—Layered products characterised by the relation between layers; Layered products characterised by the relative orientation of features between layers, or by the relative values of a measurable parameter between layers, i.e. products comprising layers having different physical, chemical or physicochemical properties; Layered products characterised by the interconnection of layers
    • B32B7/04—Interconnection of layers
    • B32B7/12—Interconnection of layers using interposed adhesives or interposed materials with bonding properties
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J123/00—Adhesives based on homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Adhesives based on derivatives of such polymers
    • C09J123/02—Adhesives based on homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Adhesives based on derivatives of such polymers not modified by chemical after-treatment
    • C09J123/04—Homopolymers or copolymers of ethene
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J123/00—Adhesives based on homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Adhesives based on derivatives of such polymers
    • C09J123/02—Adhesives based on homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Adhesives based on derivatives of such polymers not modified by chemical after-treatment
    • C09J123/10—Homopolymers or copolymers of propene
    • C09J123/14—Copolymers of propene
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J123/00—Adhesives based on homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Adhesives based on derivatives of such polymers
    • C09J123/26—Adhesives based on homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Adhesives based on derivatives of such polymers modified by chemical after-treatment
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J7/00—Adhesives in the form of films or foils
    • C09J7/20—Adhesives in the form of films or foils characterised by their carriers
    • C09J7/29—Laminated material
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J7/00—Adhesives in the form of films or foils
    • C09J7/30—Adhesives in the form of films or foils characterised by the adhesive composition
    • C09J7/35—Heat-activated
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2205/00—Polymer mixtures characterised by other features
    • C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J2301/00—Additional features of adhesives in the form of films or foils
    • C09J2301/30—Additional features of adhesives in the form of films or foils characterized by the chemical, physicochemical or physical properties of the adhesive or the carrier
    • C09J2301/304—Additional features of adhesives in the form of films or foils characterized by the chemical, physicochemical or physical properties of the adhesive or the carrier the adhesive being heat-activatable, i.e. not tacky at temperatures inferior to 30°C

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Adhesives Or Adhesive Processes (AREA)
  • Laminated Bodies (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Health & Medical Sciences (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)

Abstract

提供適合用於與聚烯烴樹脂基材或極性材料之黏著，且可低溫黏著之黏著劑組成物及熱熔黏著劑。 一種黏著劑組成物，含有酸改性聚烯烴(A)、未官能化聚烯烴(B)及聚乙烯(C)，且熔點為70~140℃。Provides adhesive compositions and hot-melt adhesives suitable for adhesion to polyolefin resin substrates or polar materials and capable of low-temperature adhesion. An adhesive composition contains acid-modified polyolefin (A), unfunctionalized polyolefin (B) and polyethylene (C), and has a melting point of 70-140°C.

Description

黏著劑組成物及熱熔黏著劑Adhesive composition and hot melt adhesive

本發明係關於使用了聚烯烴系之樹脂的黏著劑組成物，尤其是適合用於聚烯烴樹脂基材與極性材料之黏著的熱熔黏著劑。The present invention relates to an adhesive composition using a polyolefin resin, especially a hot melt adhesive suitable for the adhesion of a polyolefin resin substrate and a polar material.

聚丙烯、聚乙烯等聚烯烴材料因為容易取得且成形加工性優良，而使用於各種產業領域中。然而，聚烯烴因為分子內不具有極性基而於化學方面為惰性且為黏著性極差之材料。一般會使用有機溶劑系黏著劑進行黏著，但近年來因為對於有機溶劑使用的規定變得越來越嚴格，而有各種不使用有機溶劑來進行黏著之研究。熱熔黏著劑因為操作性簡便且容易處理而被廣泛地使用作為無溶劑黏著的一種方法。Polyolefin materials such as polypropylene and polyethylene are used in various industrial fields because they are easy to obtain and have excellent moldability. However, polyolefins are chemically inert and have extremely poor adhesion because they do not have polar groups in the molecule. Generally, organic solvent-based adhesives are used for adhesion. However, in recent years, because the regulations on the use of organic solvents have become stricter, various studies have been conducted on adhesion without using organic solvents. Hot melt adhesives are widely used as a method of solvent-free adhesion because of their ease of handling and ease of handling.

就使用了聚烯烴樹脂之黏著成分而言，有人提出了於酸改性聚烯烴樹脂中摻合乙烯-乙烯醇共聚物樹脂而得之酸改性聚烯烴樹脂組成物(專利文獻1)。As an adhesive component using a polyolefin resin, an acid-modified polyolefin resin composition obtained by blending an ethylene-vinyl alcohol copolymer resin with an acid-modified polyolefin resin has been proposed (Patent Document 1).

此外，就不使聚烯烴樹脂基材有損傷且可低溫黏著之方法而言，有人提出了於α-烯烴共聚物摻合增黏劑之方法(專利文獻2)。 [先前技術文獻] [專利文獻]In addition, as a method for enabling low-temperature adhesion without causing damage to a polyolefin resin substrate, a method of blending a tackifier with an α-olefin copolymer has been proposed (Patent Document 2). [Prior Art Literature] [Patent Literature]

[專利文獻1]日本專利3232317號公報 [專利文獻2]日本特開平10-046121號公報[Patent Document 1] Japanese Patent No. 3232317 [Patent Document 2] Japanese Patent Application Laid-Open No. 10-046121

[發明所欲解決之課題] 然而，專利文獻1記載之方法的情況，並沒有考慮到酸改性聚烯烴樹脂組成物之熔點，若酸改性聚烯烴樹脂組成物之熔點接近基材(被黏著體)之熔點，於熱黏著時有對基材造成損傷之虞，限制了使用方法。此外，就專利文獻2記載之方法，有增黏劑滲出之問題，或藉由擠製機進行混練時，熔點過低造成難以固化之問題。[Problem to be Solved by the Invention] However, in the case of the method described in Patent Document 1, the melting point of the acid-modified polyolefin resin composition is not considered, and if the melting point of the acid-modified polyolefin resin composition is close to the base material (which is The melting point of the adhesive) may cause damage to the substrate during thermal bonding, which limits the method of use. In addition, in the method described in Patent Document 2, there is a problem that the tackifier bleeds out, and when it is kneaded by an extruder, the melting point is too low, which makes it difficult to cure.

本發明係考慮上述觀點所產生者，目的為提供一種未摻合增黏劑，但藉由含有特定之酸改性聚丙烯、未官能化聚丙烯及聚乙烯而適合用於與聚烯烴基材或極性材料之黏著，進一步地藉由使其為特定範圍之熔點，而可低溫(140℃以下)黏著的熱熔黏著劑。 [解決課題之手段]The present invention was conceived in consideration of the above-mentioned viewpoints, and an object of the present invention is to provide an unmixed tackifier, which is suitable for use with polyolefin substrates by containing specific acid-modified polypropylene, unfunctionalized polypropylene and polyethylene. Or the adhesion of polar materials, and further by making the melting point in a specific range, a hot melt adhesive that can be adhered at low temperature (below 140°C). [Means of Solving Problems]

為了達成上述課題，本發明者經深入地研究而提出以下之發明。也就是說本發明係使用了以下所示之聚烯烴系之樹脂的黏著劑組成物，及使用該黏著劑組成物之熱熔黏著劑。In order to achieve the above-mentioned subject, the inventors of the present invention have made intensive studies to propose the following inventions. That is, the present invention is an adhesive composition using the polyolefin-based resin shown below, and a hot-melt adhesive using the adhesive composition.

一種黏著劑組成物，含有酸改性聚丙烯(A)、未官能化聚丙烯(B)及聚乙烯(C)，且熔點為70~140℃。An adhesive composition contains acid-modified polypropylene (A), unfunctionalized polypropylene (B) and polyethylene (C), and has a melting point of 70-140° C.

本發明之黏著劑組成物相對於酸改性聚丙烯(A)100質量份，宜含有未官能化聚丙烯(B)140~1500質量份，及聚乙烯(C)10~600質量份。The adhesive composition of the present invention preferably contains 140-1500 parts by mass of unfunctionalized polypropylene (B) and 10-600 parts by mass of polyethylene (C) relative to 100 parts by mass of acid-modified polypropylene (A).

含有上述之黏著劑組成物的熱熔黏著劑及藉由該熱熔黏著劑黏著而得之聚烯烴樹脂基材與極性材料的疊層體。 [發明之效果]A hot-melt adhesive containing the above-mentioned adhesive composition, and a laminate of a polyolefin resin base material and a polar material obtained by adhering to the hot-melt adhesive. [Effect of invention]

本發明之黏著劑組成物因為含有酸改性聚丙烯、未官能化聚丙烯及聚乙烯，且熔點為70~140℃，於將聚烯烴樹脂基材等低熔點基材進行熱黏著時不會使聚烯烴樹脂基材損傷，且可進行140℃以下之低溫黏著。此外，具有與聚烯烴樹脂基材之高黏著性。Because the adhesive composition of the present invention contains acid-modified polypropylene, unfunctionalized polypropylene and polyethylene, and has a melting point of 70-140° C., it does not work when thermally adhering low-melting-point substrates such as polyolefin resin substrates. It can damage the polyolefin resin base material, and can carry out low temperature adhesion below 140 ℃. In addition, it has high adhesion to polyolefin resin substrates.

以下針對本發明之實施形態進行詳細地說明。Hereinafter, embodiments of the present invention will be described in detail.

＜酸改性聚丙烯(A)＞ 本發明使用之酸改性聚丙烯(A)並沒有限定，藉由將α,β-不飽和羧酸及其酸酐之至少一種對於均聚丙烯及丙烯-α-烯烴共聚物之至少一種進行接枝(graft)(以下也稱為酸改性)而獲得。<Acid-modified polypropylene (A)> The acid-modified polypropylene (A) used in the present invention is not limited. At least one of the α-olefin copolymers is obtained by grafting (hereinafter also referred to as acid modification).

丙烯-α-烯烴共聚物係將丙烯作為主體將α-烯烴與其進行共聚合而得者。就α-烯烴而言，例如乙烯、1-丁烯、1-庚烯、1-辛烯、4-甲基-1-戊烯、乙酸乙烯酯等，可使用一種或數種。此等之α-烯烴中，宜為乙烯、1-丁烯。丙烯-α-烯烴共聚物之丙烯成分與α-烯烴成分之間的比率並沒有限定，丙烯成分宜為50莫耳%以上，更宜為70莫耳%以上。The propylene-α-olefin copolymer is obtained by copolymerizing an α-olefin with propylene as a main body. As for the α-olefin, for example, ethylene, 1-butene, 1-heptene, 1-octene, 4-methyl-1-pentene, vinyl acetate, etc., one or several kinds can be used. Among these α-olefins, ethylene and 1-butene are preferable. The ratio between the propylene content and the α-olefin content of the propylene-α-olefin copolymer is not limited, but the propylene content is preferably 50 mol % or more, more preferably 70 mol % or more.

就α,β-不飽和羧酸及其酸酐之至少1種而言，可舉例如馬來酸、伊康酸、檸康酸及此等之酸酐。此等中宜為酸酐，更宜為馬來酸酐。具體而言，可列舉馬來酸酐改性聚丙烯、馬來酸酐改性丙烯-乙烯共聚物、馬來酸酐改性丙烯-丁烯共聚物、馬來酸酐改性丙烯-乙烯-丁烯共聚物等，此等酸改性聚丙烯可使用1種或組合2種以上來使用。As at least 1 type of α,β-unsaturated carboxylic acid and its anhydride, maleic acid, itaconic acid, citraconic acid, and these acid anhydrides can be mentioned, for example. Among these, acid anhydride is preferred, and maleic anhydride is more preferred. Specifically, maleic anhydride-modified polypropylene, maleic anhydride-modified propylene-ethylene copolymer, maleic anhydride-modified propylene-butene copolymer, and maleic anhydride-modified propylene-ethylene-butene copolymer may be mentioned. etc., these acid-modified polypropylenes can be used individually or in combination of 2 or more types.

考慮極性材料與聚烯烴樹脂基材之黏著性的觀點，酸改性聚丙烯(A)之酸價(mgKOH/g-resin)宜為3mgKOH/g-resin以上，更宜為6mgKOH/g-resin以上，進一步宜為9mgKOH/g-resin以上。若酸價為未達3mgKOH/g-resin，有時會損害與極性材料之黏著性。此外，宜為50mgKOH/g-resin以下，更宜為30mgKOH/g-resin以下。若超過50mgKOH/g-resin有時會使其與聚烯烴樹脂基材的黏著性低落。Considering the adhesion between polar materials and polyolefin resin substrates, the acid value (mgKOH/g-resin) of acid-modified polypropylene (A) is preferably 3 mgKOH/g-resin or more, more preferably 6 mgKOH/g-resin Above, more preferably 9 mgKOH/g-resin or more. If the acid value is less than 3mgKOH/g-resin, the adhesion to polar materials may be impaired. Further, it is preferably 50 mgKOH/g-resin or less, and more preferably 30 mgKOH/g-resin or less. If it exceeds 50 mgKOH/g-resin, the adhesiveness to a polyolefin resin base material may fall.

酸改性聚丙烯(A)之熔點宜為65℃以上，更宜為80℃以上，進一步宜為90℃以上。若未達上述之值，將難以進行造粒。此外，宜為140℃以下，更宜為130℃以下。若超過上述之值，有時會損害低溫熱封性。為了獲得上述熔點之酸改性聚丙烯(A)，宜於原料中使用低熔點之未官能化聚丙烯。未官能化聚丙烯之熔點宜為70℃以上，更宜為95℃以上，宜為145℃以下，更宜為135℃以下。The melting point of the acid-modified polypropylene (A) is preferably 65°C or higher, more preferably 80°C or higher, and further preferably 90°C or higher. If the above-mentioned value is not reached, it will be difficult to granulate. Further, it is preferably 140°C or lower, more preferably 130°C or lower. If the above-mentioned value is exceeded, the low-temperature heat sealability may be impaired. In order to obtain the acid-modified polypropylene (A) with the above-mentioned melting point, it is suitable to use unfunctionalized polypropylene with a low melting point as the raw material. The melting point of the unfunctionalized polypropylene is preferably 70°C or higher, more preferably 95°C or higher, preferably 145°C or lower, and more preferably 135°C or lower.

酸改性聚丙烯(A)之熔點宜比後述之未官能化聚丙烯(B)更低5~10℃。The melting point of the acid-modified polypropylene (A) is preferably 5 to 10°C lower than that of the unfunctionalized polypropylene (B) described later.

酸改性聚丙烯(A)在230℃之熔融黏度宜為1000mPa･s以上，更宜為2000mPa･s以上。若未達上述之值，將難以進行造粒。此外，宜為20000mPa･s以下，更宜為10000mPa･s以下。若超過上述之值，晾置時間(open time)會變短，操作性變差。The melt viscosity of the acid-modified polypropylene (A) at 230°C is preferably 1000 mPa･s or more, more preferably 2000 mPa･s or more. If the above-mentioned value is not reached, it will be difficult to granulate. In addition, it is preferably 20000 mPa･s or less, more preferably 10000 mPa･s or less. If the above-mentioned value is exceeded, the open time (open time) will be shortened, and the operability will be deteriorated.

酸改性聚丙烯(A)宜為結晶性。結晶性與非晶性相比，因為凝聚力強，且黏著性或耐藥品性優良而較為有利。此處，本發明所指之結晶性，係指使用差示掃描量熱計(DSC)，以20℃/分鐘從-100℃升溫至250℃，於該升溫過程中有展示明確之熔解峰者。The acid-modified polypropylene (A) is preferably crystalline. Crystallinity is more advantageous than amorphous because of strong cohesion and excellent adhesion or chemical resistance. Here, the crystallinity referred to in the present invention refers to a temperature rising from -100°C to 250°C at 20°C/min using a differential scanning calorimeter (DSC), and showing a clear melting peak during the heating process .

就酸改性聚丙烯(A)之製造方法而言，沒有特別之限定，可舉例如自由基接枝反應(也就是對於為主鏈之聚合物生成自由基，將該自由基作為聚合起始點使不飽和羧酸及酸酐進行接枝聚合之反應)等。There are no particular limitations on the production method of the acid-modified polypropylene (A), for example, a radical grafting reaction (that is, a radical is generated for the polymer of the main chain, and the radical is used as a polymerization starter). Point to make unsaturated carboxylic acid and acid anhydride carry out the reaction of graft polymerization) and so on.

就自由基產生劑而言，沒有特別之限定，宜使用有機過氧化物。就有機過氧化物而言，可列舉過氧化鄰苯二甲酸二第三丁酯、第三丁基過氧化氫、過氧化二異丙苯、過氧化苯甲醯、過氧化苯甲酸第三丁酯、過氧化-2-乙基己酸第三丁酯、過氧化特戊酸第三丁酯、過氧化甲乙酮、二第三丁基過氧化物、過氧化月桂醯等過氧化物;偶氮雙異丁腈、偶氮雙異丙腈等偶氮腈類。The radical generator is not particularly limited, and an organic peroxide is preferably used. The organic peroxides include di-tert-butyl peroxyphthalate, tert-butyl hydroperoxide, dicumyl peroxide, benzyl peroxide, and tert-butyl peroxybenzoate. Peroxides such as tert-butyl peroxy-2-ethylhexanoate, tert-butyl peroxypivalate, methyl ethyl ketone peroxide, di-tert-butyl peroxide, lauryl peroxide; azo Azonitriles such as bisisobutyronitrile and azobisisopropionitrile.

＜未官能化聚丙烯(B)＞ 於本發明使用之未官能化聚丙烯(B)雖然沒有特別之限定，為均聚丙烯或丙烯-α-烯烴共聚物，係指未進行上述之酸改性，或即使進行了酸改性時酸價為未達3mgKOH/g-resin者。宜為酸價為2mgKOH/g-resin以下，更宜為1mgKOH/g-resin以下，進一步宜為0.1mgKOH/g-resin以下。<Unfunctionalized polypropylene (B)> Although the unfunctionalized polypropylene (B) used in the present invention is not particularly limited, it is a homopolypropylene or a propylene-α-olefin copolymer, which means that the above-mentioned acid modification has not been carried out. properties, or the acid value is less than 3 mgKOH/g-resin even after acid modification. The acid value is preferably 2 mgKOH/g-resin or less, more preferably 1 mgKOH/g-resin or less, and further preferably 0.1 mgKOH/g-resin or less.

丙烯-α-烯烴共聚物係將丙烯作為主體與α-烯烴進行共聚合而得者。就α-烯烴而言，例如乙烯、1-丁烯、1-庚烯、1-辛烯、4-甲基-1-戊烯、乙酸乙烯酯等，可使用一種或數種。此等之α-烯烴中，宜為乙烯、1-丁烯。丙烯-α-烯烴共聚物之丙烯成分與α-烯烴成分之間之比率雖然沒有限定，丙烯成分宜為50莫耳%以上，更宜為70莫耳%以上。The propylene-α-olefin copolymer is obtained by copolymerizing propylene as a main body and an α-olefin. As for the α-olefin, for example, ethylene, 1-butene, 1-heptene, 1-octene, 4-methyl-1-pentene, vinyl acetate, etc., one or several kinds can be used. Among these α-olefins, ethylene and 1-butene are preferable. Although the ratio between the propylene content and the α-olefin content of the propylene-α-olefin copolymer is not limited, the propylene content is preferably 50 mol % or more, more preferably 70 mol % or more.

未官能化聚丙烯(B)係上述之酸改性以外未進行氫氧基、羧基、環氧基等極性基之接枝較為理想。此處，未進行接枝係指接枝量為未達0.3質量%，宜為0.2質量%以下，更宜為0.1質量%以下，進一步宜為0.01質量%以下。The unfunctionalized polypropylene (B) is preferably not grafted with polar groups such as hydroxyl groups, carboxyl groups, and epoxy groups other than the above acid modification. Here, the grafting amount is less than 0.3 mass %, preferably 0.2 mass % or less, more preferably 0.1 mass % or less, and further preferably 0.01 mass % or less.

未官能化聚丙烯(B)之熔點宜為70℃以上，更宜為95℃以上。若未達上述之值，將難以造粒。此外，宜為145℃以下，更宜為135℃以下，若超過上述之值，會損害低溫熱封性。The melting point of the unfunctionalized polypropylene (B) is preferably 70°C or higher, more preferably 95°C or higher. If the above value is not reached, it will be difficult to granulate. Further, it is preferably 145° C. or lower, more preferably 135° C. or lower, and if it exceeds the above-mentioned value, the low-temperature heat sealability will be impaired.

未官能化聚丙烯(B)之於230℃之熔體流動速率(MFR)宜為1g/10分鐘以上，更宜為2g/10分鐘以上。若未達上述之值，晾置時間會變短。此外，宜為1000g/10分鐘以下，更宜為500g/10分鐘以下。若超過上述之值，將難以進行造粒。The melt flow rate (MFR) at 230°C of the unfunctionalized polypropylene (B) is preferably 1 g/10 minutes or more, more preferably 2 g/10 minutes or more. If the above value is not reached, the drying time will be shortened. Moreover, it is preferable that it is 1000 g/10 minutes or less, and it is more preferable that it is 500 g/10 minutes or less. If it exceeds the above-mentioned value, it becomes difficult to granulate.

相對於酸改性聚丙烯(A)100質量份，未官能化聚丙烯(B)之含量宜為140質量份以上，更宜為160質量份以上，進一步宜為180質量份以上。若未達上述之值，有時對於聚烯烴樹脂基材之黏著性低落。此外，宜為1500質量份以下，更宜為1000質量份以下，進一步宜為800質量份以下。若超過上述之值，與極性材料之黏著性低落，較不理想。The content of the unfunctionalized polypropylene (B) is preferably 140 parts by mass or more, more preferably 160 parts by mass or more, and further preferably 180 parts by mass or more relative to 100 parts by mass of the acid-modified polypropylene (A). If it is less than the above-mentioned value, the adhesiveness to a polyolefin resin base material may fall. Moreover, 1500 mass parts or less are preferable, 1000 mass parts or less are more preferable, and 800 mass parts or less are more preferable. If it exceeds the above-mentioned value, the adhesion to polar materials will be lowered, which is not ideal.

＜聚乙烯(C)＞ 於本發明中使用之聚乙烯(C)種類並沒有限定，可列舉高密度聚乙烯、低密度聚乙烯等。考慮容易控制黏著劑組成物之熔點宜為低密度聚乙烯。<Polyethylene (C)> The kind of polyethylene (C) used by this invention is not limited, High density polyethylene, a low density polyethylene, etc. are mentioned. Considering that it is easy to control the melting point of the adhesive composition, it is appropriate to use low-density polyethylene.

聚乙烯(C)雖然沒有限定，宜為均聚乙稀或乙烯-α-烯烴共聚物。就α-烯烴而言，例如丙烯、1-丁烯、1-庚烯、1-辛烯、4-甲基-1-戊烯、乙酸乙烯酯等，可使用一種或多種。此等之α-烯烴中，宜為丙烯、1-丁烯。乙烯-α-烯烴共聚物之乙烯成分與α-烯烴成分之間之比率雖然沒有限定，宜為乙烯成分為50莫耳%以上，更宜為70莫耳%以上。Although the polyethylene (C) is not limited, it is preferably a homopolyethylene or an ethylene-α-olefin copolymer. As the α-olefin, for example, propylene, 1-butene, 1-heptene, 1-octene, 4-methyl-1-pentene, vinyl acetate, etc., one or more kinds can be used. Among these α-olefins, propylene and 1-butene are preferable. Although the ratio between the ethylene content and the α-olefin content of the ethylene-α-olefin copolymer is not limited, the ethylene content is preferably 50 mol % or more, and more preferably 70 mol % or more.

聚乙烯(C)宜為未進行上述之酸改性，或即使進行了酸改性後其酸價為未達3mgKOH/g-resin者。更宜為酸價為2mgKOH/g-resin以下，進一步宜為1mgKOH/g-resin以下，尤其宜為0.1mgKOH/g-resin以下。Polyethylene (C) is preferably not acid-modified as described above, or even if acid-modified, its acid value is less than 3 mgKOH/g-resin. The acid value is more preferably 2 mgKOH/g-resin or less, more preferably 1 mgKOH/g-resin or less, and particularly preferably 0.1 mgKOH/g-resin or less.

聚乙烯(C)之密度沒有特別之限定，宜為0.910g/cm3 以上未達0.930g/cm3 。The density of polyethylene (C) is not particularly limited, but is preferably 0.910 g/cm 3 or more and less than 0.930 g/cm 3 .

聚乙烯(C)之熔點宜為90℃以上，更宜為95℃以上。聚乙烯(C)之熔點若低於90℃，將難以造粒，考慮生產性之觀點並不理想。此外，宜為130℃以下，更宜為120℃以下。若超過130℃，有時會損害低溫黏著性之特徵。The melting point of polyethylene (C) is preferably 90°C or higher, more preferably 95°C or higher. If the melting point of polyethylene (C) is lower than 90° C., it will be difficult to granulate, which is not preferable from the viewpoint of productivity. Further, it is preferably 130°C or lower, more preferably 120°C or lower. If it exceeds 130°C, the characteristics of low temperature adhesion may be impaired.

聚乙烯(C)係未進行上述酸改性，或即使進行了酸改性時其酸價為1mgKOH/g-resin以下較為理想。更宜為0.1mgKOH/g-resin以下。Polyethylene (C) is preferably not acid-modified as described above, or even if acid-modified, its acid value is preferably 1 mgKOH/g-resin or less. More preferably, it is 0.1 mgKOH/g-resin or less.

聚乙烯(C)之於190℃之熔體流動速率(MFR)宜為0.1g/10分鐘以上，更宜為0.2g/10分鐘以上。若未達上述之值，有時會使晾置時間變短，操作性變差。此外，宜為100g/10分鐘以上，更宜為50g/10分鐘以下。若超過上述之值，則難以進行造粒。The melt flow rate (MFR) at 190°C of the polyethylene (C) is preferably 0.1 g/10 minutes or more, more preferably 0.2 g/10 minutes or more. If the above-mentioned value is not reached, the open time may be shortened, and the operability may be deteriorated. Moreover, it is preferable that it is 100 g/10 minutes or more, and it is more preferable that it is 50 g/10 minutes or less. If it exceeds the above-mentioned value, it becomes difficult to granulate.

相對於酸改性聚丙烯(A)100質量份，聚乙烯(C)之含量宜為10質量份以上，更宜為15質量份以上，進一步宜為20質量份以上。若未達上述之值將難以進行造粒，考慮生產性之觀點較不理想。此外，宜為600質量份以下，更宜為400質量份以下，進一步宜為200質量份以下。若超過上述之值，則與極性材料之黏著性低落，較不理想。The content of polyethylene (C) is preferably 10 parts by mass or more, more preferably 15 parts by mass or more, and further preferably 20 parts by mass or more, relative to 100 parts by mass of acid-modified polypropylene (A). If it is less than the above-mentioned value, it will be difficult to granulate, and it is not preferable from the viewpoint of productivity. Moreover, 600 mass parts or less are preferable, 400 mass parts or less are more preferable, and 200 mass parts or less are more preferable. If it exceeds the above-mentioned value, the adhesiveness with the polar material will decrease, which is not preferable.

＜黏著劑組成物＞ 本發明之黏著劑組成物係含有酸改性聚丙烯(A)、未官能化聚丙烯(B)及聚乙烯(C)，且熔點為70~140℃之組合物。<Adhesive composition> The adhesive composition of the present invention contains acid-modified polypropylene (A), unfunctionalized polypropylene (B) and polyethylene (C), and has a melting point of 70 to 140°C.

藉由含有上述指定量之酸改性聚丙烯(A)、未官能化聚丙烯(B)及聚乙烯(C)，可獲得熔點為70~140℃之組成物。By containing the above-specified amounts of acid-modified polypropylene (A), unfunctionalized polypropylene (B) and polyethylene (C), a composition having a melting point of 70 to 140° C. can be obtained.

本發明之黏著劑組成物之熔點宜為75℃以上，更宜為80℃以上，進一步宜為90℃以上。黏著劑組成物之熔點若未達70℃，有時變得難以造粒，考慮生產性之觀點較不理想。此外，宜為135℃以下，更宜為130℃以下，進一步宜為120℃以下。熔點若超過140℃，會損害低溫黏著性之特徵。The melting point of the adhesive composition of the present invention is preferably 75°C or higher, more preferably 80°C or higher, and further preferably 90°C or higher. If the melting point of the adhesive composition is less than 70° C., it may become difficult to granulate, which is not preferable from the viewpoint of productivity. Further, it is preferably 135°C or lower, more preferably 130°C or lower, and further preferably 120°C or lower. If the melting point exceeds 140°C, the characteristics of low temperature adhesion will be impaired.

本發明中，沒有特別之限定，可將上述酸改性聚丙烯(A)、未官能化聚丙烯(B)及聚乙烯(C)進行熔融混練而可獲得均勻之黏著劑組成物。熔融混練通常可使用塑膠用熔融混練機，例如可使用單軸、二軸之混練擠製機、加熱型熔融攪拌槽等。In the present invention, it is not particularly limited, and the above-mentioned acid-modified polypropylene (A), unfunctionalized polypropylene (B) and polyethylene (C) can be melt-kneaded to obtain a uniform adhesive composition. Melt kneading can usually be performed using a plastic melt kneader, for example, a single-shaft or two-shaft kneading extruder, a heating-type melting and stirring tank, and the like can be used.

本發明之黏著劑組成物宜為實質上不含有增黏劑。實質上不含有增黏劑係指黏著劑組成物中增黏劑宜為1質量%以下，更宜為0.1質量%以下，進一步宜為0質量%。因為實質上不含有增黏劑也沒有滲出之問題，可獲得容易固化且生產性高之黏著劑組成物。就增黏劑而言，可舉例如萜烯(terpene)系樹脂、松香系樹脂、或石油系樹脂。The adhesive composition of the present invention preferably contains substantially no tackifier. The fact that a tackifier is not substantially contained means that the amount of the tackifier in the adhesive composition is preferably 1 mass % or less, more preferably 0.1 mass % or less, and further preferably 0 mass %. Since it does not contain a tackifier substantially and there is no problem of exudation, an easily curable and highly productive adhesive composition can be obtained. As a tackifier, a terpene-type resin, a rosin-type resin, or a petroleum-type resin is mentioned, for example.

＜熱熔黏著劑＞ 本發明之熱熔黏著劑係含有上述黏著劑組成物且不含有有機溶劑之組成物。熱熔黏著劑中，宜含有上述黏著劑組成物90質量%以上，更宜含有95質量%以上，進一步宜含有100質量%。若過少有時會使其與聚烯烴樹脂基材或極性材料之黏著性低落。<Hot-melt adhesive> The hot-melt adhesive of the present invention contains the above-mentioned adhesive composition and does not contain an organic solvent. In the hot-melt adhesive, the above-mentioned adhesive composition is preferably contained at 90% by mass or more, more preferably at 95% by mass or more, and further preferably at 100% by mass. If the amount is too small, the adhesion to the polyolefin resin base material or polar material may be reduced.

本發明之熱熔黏著劑可在不損害本發明之性能之範圍摻合各種添加劑。就添加劑而言沒有特別之限制，使用阻燃劑、顏料、抗結塊劑(antiblocking agent)等較為理想。The hot-melt adhesive of the present invention can incorporate various additives within the range that does not impair the performance of the present invention. The additives are not particularly limited, and flame retardants, pigments, antiblocking agents, etc. are preferably used.

＜聚烯烴樹脂基材＞ 就聚烯烴樹脂基材而言，可從以往公知之聚烯烴樹脂中適當地選擇。例如，雖然沒有特別之限定，可使用聚乙烯、聚丙烯、乙烯-丙烯共聚物等。其中，宜使用均聚丙烯板(以下也稱為PP)。其厚度沒有特別之限定，宜為0.1~5mm，更宜為0.5~3mm，進一步宜為1~2mm。其中，於聚烯烴樹脂基材中，因應需求可摻合顏料或各種添加物。<Polyolefin resin substrate> The polyolefin resin substrate can be appropriately selected from conventionally known polyolefin resins. For example, although not particularly limited, polyethylene, polypropylene, ethylene-propylene copolymer and the like can be used. Among them, a homopolypropylene plate (hereinafter also referred to as PP) is preferably used. The thickness is not particularly limited, but is preferably 0.1 to 5 mm, more preferably 0.5 to 3 mm, and further preferably 1 to 2 mm. Among them, in the polyolefin resin base material, pigments or various additives can be blended according to requirements.

＜極性材料＞ 本發明之極性材料係沒有特別之限定，可列舉金屬基材、極性樹脂基材等。其中宜為金屬基材。<Polar material> The polar material of the present invention is not particularly limited, and examples thereof include metal substrates, polar resin substrates, and the like. Among them, metal substrates are suitable.

就金屬基材而言，沒有特別之限定，例如可使用鋁、銅、鋼鐵、SUS、鎂、鋅、杜拉鋁(Duralumin)等各種金屬及該合金，且就該形狀而言，可選擇金屬板、壓延板、板、管、罐、蓋等任意之形狀。一般而言，考慮加工性等觀點宜為鋁板。此外，雖然會根據使用目的而有所不同，一般而言使用厚度為0.01~10mm，宜為0.02~5mm之片狀。此外，此等金屬基材之表面可預先施以表面處理，也可保持為未處理之狀態。The metal base material is not particularly limited, for example, various metals such as aluminum, copper, steel, SUS, magnesium, zinc, Duralumin, and the alloy thereof can be used, and the shape can be selected from a metal Any shape such as plate, rolled plate, plate, tube, tank, lid, etc. Generally speaking, it is preferable to use an aluminum plate in consideration of workability and the like. In addition, although it varies according to the purpose of use, in general, the thickness is 0.01 to 10 mm, preferably 0.02 to 5 mm. In addition, the surfaces of these metal substrates may be pre-treated or left untreated.

就極性樹脂基材而言，雖然沒有特別之限定，例如可使用耐綸、乙烯/乙烯醇共聚合樹脂(EVOH)、聚對苯二甲酸乙二酸酯(PET)等極性高之塑膠系材料，且就該形狀而言可選擇任意之形狀。此外，雖然根據使用目的而有所不同，一般而言使用厚度為0.01~10mm，宜為0.02~5mm之片狀。另外，此等極性樹脂基材之表面可預先施以表面處理，也可保持為未處理之狀態。為任一情況皆可發揮同等之效果。As far as the polar resin substrate is concerned, although it is not particularly limited, for example, nylon, ethylene/vinyl alcohol copolymer resin (EVOH), polyethylene terephthalate (PET) and other highly polar plastic materials can be used , and any shape can be selected for the shape. In addition, although it differs according to the purpose of use, in general, a thickness of 0.01 to 10 mm, preferably 0.02 to 5 mm, is used. In addition, the surface of these polar resin substrates may be pre-treated with a surface treatment, or may be kept in an untreated state. In either case, the same effect can be achieved.

＜疊層體＞ 本發明之疊層體係將極性材料與聚烯烴樹脂基材藉由本發明之熱熔黏著劑進行疊層(極性材料/黏著劑層/聚烯烴樹脂基材)而得者。<Laminated body> The lamination system of the present invention is obtained by laminating a polar material and a polyolefin resin substrate with the hot-melt adhesive of the present invention (polar material/adhesive layer/polyolefin resin substrate).

就疊層方法而言，可使用以往習知之層合(laminate)製造技術。例如，雖然沒有特別之限定，使用塗布輥或塗布棒等適當之塗布工具將熱熔黏著劑塗布於極性材料之表面，於在極性材料之表面形成之黏著劑層處於熔融狀態的期間，將聚烯烴樹脂基材進行疊層黏著於該塗布面可獲得疊層體。熱壓接之溫度沒有特別之限定，宜為130℃以上，更宜為140℃以上，宜為160℃以下，更宜為150℃以下。熱壓接之壓力沒有特別之限定，宜為0.09MPa以上，更宜為0.1MPa以上，宜為0.12MPa以下，更宜為0.11MPa以下。 藉由上述熱熔黏著劑形成之黏著劑層之厚度沒有特別之限定，宜為10~100μm，更宜為20~80μm，進一步宜為30~50μm。As the lamination method, conventionally known laminate manufacturing techniques can be used. For example, although not particularly limited, the hot-melt adhesive is applied to the surface of the polar material by using a suitable coating tool such as a coating roller or a coating bar, and the adhesive layer formed on the surface of the polar material is in a molten state. The olefin resin substrate is laminated and adhered to the coated surface to obtain a laminated body. The temperature of thermocompression bonding is not particularly limited, but is preferably 130°C or higher, more preferably 140°C or higher, preferably 160°C or lower, and more preferably 150°C or lower. The pressure of thermocompression bonding is not particularly limited, but is preferably 0.09 MPa or more, more preferably 0.1 MPa or more, preferably 0.12 MPa or less, and more preferably 0.11 MPa or less. The thickness of the adhesive layer formed by the above-mentioned hot melt adhesive is not particularly limited, but is preferably 10 to 100 μm, more preferably 20 to 80 μm, and further preferably 30 to 50 μm.

以下列舉實施例來更詳細地說明本發明。惟，本發明並不僅限定於實施例。實施例中及比較例中僅以「份」表示者係表示質量份。The following examples are given to illustrate the present invention in more detail. However, the present invention is not limited only to the examples. In Examples and Comparative Examples, what is only represented by "parts" means parts by mass.

(製造例1) 於1L加熱釜中，加入熔點100℃之未官能化聚丙烯(未官能化PO-B1、丙烯-丁烯共聚物(三井化學公司製「TAFMER(註冊商標)XM7090」))100質量份、甲苯150質量份及馬來酸酐10質量份，藉由升溫至130℃使其均勻地溶解。在130℃於未官能化PO-B1溶液中加入二第三丁基過氧化物4質量份，升溫至140℃後進一步地攪拌3小時。之後，將獲得之反應液冷卻後，倒入至裝有大量之甲乙酮之容器中，使樹脂析出。之後，藉由將含有該樹脂之液體進行離心分離，使分枝聚合了馬來酸酐之酸改性聚丙烯與(聚)馬來酸酐及低分子量物固液分離，進行純化。之後，藉由使其在減壓下於70℃乾燥5小時，而獲得馬來酸酐改性聚丙烯(酸改性PO-A1、酸價11mgKOH/g-resin、熔點95℃、熔融黏度3000mPa･s)。(Production Example 1) Unfunctionalized polypropylene (unfunctionalized PO-B1, propylene-butene copolymer ("TAFMER (registered trademark) XM7090" manufactured by Mitsui Chemicals Co., Ltd.) with a melting point of 100° C.) was placed in a 1 L heating pot. 100 parts by mass, 150 parts by mass of toluene, and 10 parts by mass of maleic anhydride were uniformly dissolved by raising the temperature to 130°C. 4 parts by mass of di-tert-butyl peroxide was added to the unfunctionalized PO-B1 solution at 130°C, the temperature was raised to 140°C, and the mixture was further stirred for 3 hours. Then, after cooling the obtained reaction liquid, it was poured into a container containing a large amount of methyl ethyl ketone, and the resin was precipitated. Then, by centrifuging the liquid containing the resin, the acid-modified polypropylene with branched maleic anhydride, the (poly)maleic anhydride, and the low molecular weight substance are separated into solid-liquid and purified. Then, it was dried under reduced pressure at 70°C for 5 hours to obtain maleic anhydride-modified polypropylene (acid-modified PO-A1, acid value 11 mgKOH/g-resin, melting point 95°C, melt viscosity 3000mPa･ s).

(製造例2) 變更為熔點135℃之未官能化聚丙烯(PO-B2，日本聚丙烯公司製「WINTEC(註冊商標)PP WFW4」)以外，藉由與製造例1相同方式獲得馬來酸酐改性聚丙烯(酸改性PO-A2，酸價15mgKOH/g-resin，熔點130℃，熔融黏度3500mPa･s)。(Production Example 2) Maleic anhydride was obtained in the same manner as in Production Example 1, except that the unfunctionalized polypropylene (PO-B2, "WINTEC (registered trademark) PP WFW4" manufactured by Nippon Polypropylene Corporation) having a melting point of 135°C was changed. Modified polypropylene (acid modified PO-A2, acid value 15mgKOH/g-resin, melting point 130℃, melt viscosity 3500mPa･s).

(製造例3) 變更為熔點160℃之未官能化聚丙烯(PO-B3，Prime Polymer Co., Ltd.製「J-105G」)以外，藉由與製造例1相同方式獲得馬來酸酐改性聚丙烯(酸改性PO-A3，酸價8mgKOH/g-resin，熔點155℃，熔融黏度4000mPa･s)。(Production Example 3) A maleic anhydride modified polypropylene was obtained in the same manner as in Production Example 1 except that it was changed to an unfunctionalized polypropylene (PO-B3, "J-105G" manufactured by Prime Polymer Co., Ltd.) with a melting point of 160°C. Polypropylene (acid modified PO-A3, acid value 8mgKOH/g-resin, melting point 155℃, melt viscosity 4000mPa･s).

(製造例4) 變更為熔點75℃之未官能化聚丙烯(PO-B4，三井化學公司製「TAFMER(註冊商標)」XM7070)以外，藉由與製造例1相同方式獲得馬來酸酐改性聚丙烯(酸改性PO-A4，酸價11mgKOH/g-resin，熔點65℃，熔融黏度2500mPa･s)。(Manufacturing Example 4) Maleic anhydride modified polypropylene (PO-B4, "TAFMER (registered trademark)" XM7070 manufactured by Mitsui Chemicals Co., Ltd.) having a melting point of 75° C. was changed to obtain a maleic anhydride modification in the same manner as in Manufacturing Example 1. Polypropylene (acid modified PO-A4, acid value 11mgKOH/g-resin, melting point 65℃, melt viscosity 2500mPa･s).

(實施例1) 將10質量份作為酸改性聚丙烯(A)之酸改性PO-A1，75質量份作為未官能化聚丙烯(B)之未官能化PO-B1，15質量份作為聚乙烯(C)之PE-1藉由15mmφ二軸擠製機於160℃進行熔融混練並進行造粒，而獲得熱熔黏著劑。(Example 1) 10 parts by mass of acid-modified PO-A1 as acid-modified polypropylene (A), 75 parts by mass as unfunctionalized PO-B1 of unfunctionalized polypropylene (B), and 15 parts by mass as The PE-1 of polyethylene (C) was melt-kneaded and pelletized at 160° C. with a 15 mmφ biaxial extruder to obtain a hot-melt adhesive.

(實施例2~11、比較例1~3) 將酸改性聚丙烯(A)、未官能化聚丙烯(B)及聚乙烯(C)之種類、摻合量如表1所示進行變更，藉由與實施例1同樣之方法來進行實施例2~11、比較例1~3的製造。摻合量、黏著性及造粒評價表示於表1。(Examples 2 to 11, Comparative Examples 1 to 3) The types and blending amounts of acid-modified polypropylene (A), unfunctionalized polypropylene (B), and polyethylene (C) were changed as shown in Table 1. , by the same method as in Example 1, Examples 2 to 11 and Comparative Examples 1 to 3 were produced. Table 1 shows the blending amount, adhesiveness and granulation evaluation.

於實施例及比較例使用之未官能化聚丙烯(B)、聚乙烯(C)如同下述。 [未官能化聚丙烯(B)] 未官能化PO-B1:丙烯-丁烯共聚物(三井化學公司製「TAFMER(註冊商標)XM7090」)，熔點100℃，MFR7g/10分鐘。 未官能化PO-B2:丙烯-乙烯共聚物(日本聚丙烯公司製「WINTEC(註冊商標)WFW4」)，熔點135℃，MFR7g/10分鐘。 未官能化PO-B3:均聚丙烯(Prime Polymer Co., Ltd.製「J-105G」)，熔點160℃，MFR9g/10分鐘。 未官能化PO-B4:丙烯-丁烯共聚物(三井化學公司製「TAFMER(註冊商標)XM7070」)，熔點75℃，MFR7g/10分鐘。 [聚乙烯(C)] PE-1:低密度聚乙烯(東曹公司製「Petrothene(註冊商標)172」)，熔點110℃，密度0.920g/cm3 ，MFR0.30g/10分鐘。The unfunctionalized polypropylene (B) and polyethylene (C) used in the examples and comparative examples are as follows. [Unfunctionalized polypropylene (B)] Unfunctionalized PO-B1: propylene-butene copolymer ("TAFMER (registered trademark) XM7090" manufactured by Mitsui Chemicals Corporation), melting point 100° C., MFR 7 g/10 minutes. Unfunctionalized PO-B2: propylene-ethylene copolymer (“WINTEC (registered trademark) WFW4” manufactured by Nippon Polypropylene Corporation), melting point 135° C., MFR 7 g/10 minutes. Unfunctionalized PO-B3: homopolypropylene (“J-105G” manufactured by Prime Polymer Co., Ltd.), melting point 160° C., MFR 9 g/10 minutes. Unfunctionalized PO-B4: propylene-butene copolymer ("TAFMER (registered trademark) XM7070" manufactured by Mitsui Chemicals Corporation), melting point 75° C., MFR 7 g/10 minutes. [Polyethylene (C)] PE-1: Low-density polyethylene (“Petrothene (registered trademark) 172” manufactured by Tosoh Corporation), melting point 110° C., density 0.920 g/cm 3 , MFR 0.30 g/10 minutes.

(酸價之測定) 本發明之酸價(mgKOH/g-resin)係利用使用FT-IR(島津製作所製，FT-IR8200PC)，由藉由馬來酸酐(東京化成製)之氯仿溶液製成之檢量線獲得之係數(f)，及結晶性馬來酸酐改性聚烯烴之馬來酸酐的羰基(C=O)之伸縮峰(1780cm-1 )之吸光度(I)，依下列式算出而得之值。 酸價(mgKOH/g-resin)=[吸光度(I)×(f)×2×氫氧化鉀之分子量×1000(mg)/馬來酸酐之分子量] 馬來酸酐之分子量:98.06氫氧化鉀之分子量:56.11(Measurement of acid value) The acid value (mgKOH/g-resin) of the present invention was prepared by using FT-IR (manufactured by Shimadzu Corporation, FT-IR8200PC) from a chloroform solution of maleic anhydride (manufactured by Tokyo Chemical Industry Co., Ltd.). The coefficient (f) obtained from the calibration curve, and the absorbance (I) of the stretching peak (1780 cm -1 ) of the maleic anhydride carbonyl group (C=O) of the crystalline maleic anhydride-modified polyolefin are calculated according to the following formula and worth it. Acid value (mgKOH/g-resin) = [absorbance (I) × (f) × 2 × molecular weight of potassium hydroxide × 1000 (mg) / molecular weight of maleic anhydride] Molecular weight of maleic anhydride: 98.06 of potassium hydroxide Molecular weight: 56.11

(熔點之測定) 將樣本1g使用差示掃描量熱計(以下也稱為DSC，TA Instruments. Japan.製，Q-2000)，以20℃/分鐘之速度進行升溫熔解，並進行冷卻樹脂化，再次進行升溫熔解(2nd Run.)時，測得之吸熱峰之面積最大之極大點(觀察到多個吸熱峰時，為其中面積最大之吸熱峰的點)之值，將此值作為熔點。(Measurement of Melting Point) Using a differential scanning calorimeter (hereinafter also referred to as DSC, Q-2000, manufactured by TA Instruments. Japan.), 1 g of the sample was heated and melted at a rate of 20°C/min, and then cooled and resinized. , when the temperature rise and melting (2nd Run.) is performed again, the maximum point of the maximum endothermic peak area measured (when multiple endothermic peaks are observed, is the point of the endothermic peak with the largest area), and this value is taken as the melting point.

(熔融黏度之測定) 將樣本10g使用單一圓筒型旋轉式黏度計(BROOKFIELD VISCOMETER DV-I型)，進行升溫熔解(230℃)，在經熔融之樹脂中使轉子旋轉，從旋轉轉矩讀取產生之黏性阻力來判斷黏度(單位:mPa・s)。(Measurement of Melt Viscosity) Using a single-cylinder rotational viscometer (BROOKFIELD VISCOMETER DV-I type), 10 g of the sample was heated and melted (230°C), the rotor was rotated in the melted resin, and read from the rotational torque. Take the generated viscous resistance to judge the viscosity (unit: mPa·s).

(熔體流動速率(MFR)之測定) 使用東洋精機製作所(股)製之熔體指數測定儀，依循JIS K 7210-1(2014)，於190℃或230℃進行升溫熔解，測定以負荷2160g將樹脂組成物擠製時之排出重量，換算為每10分鐘之量(單位:g/10分鐘)來表示。(Measurement of Melt Flow Rate (MFR)) Using a melt index meter manufactured by Toyo Seiki Seisakusho Co., Ltd., in accordance with JIS K 7210-1 (2014), the temperature was increased for melting at 190°C or 230°C, and the measurement was performed with a load of 2160 g. The discharge weight at the time of extruding the resin composition is expressed as the amount per 10 minutes (unit: g/10 minutes).

(疊層體之製作) 極性材料使用鋁板(Nippon Testpanel Co.,Ltd.製，A1050P，厚度×寬×長=1.6×25×100mm)，聚烯烴樹脂基材使用聚丙烯板(Nippon Testpanel Co.,Ltd.製，PP，厚度×寬×長=1.6×25×100mm)。 藉由熱壓接將藉由實施例1~11、比較例1~3獲得之熱熔黏著劑之厚度調整成為50μm，疊層於極性材料。然後於黏著劑表面重疊聚烯烴樹脂基材，藉由在TESTER SANGYO CO,. LTD.製熱封試驗儀之圓筒溫度140℃、0.1MPa進行2分鐘之熱壓接而獲得疊層體(極性材料/黏著劑層/聚丙烯樹脂基材)。藉由拉伸剪切試驗來測定上述疊層體之黏著強度。(Production of Laminate) An aluminum plate (A1050P, manufactured by Nippon Testpanel Co., Ltd., thickness×width×length=1.6×25×100 mm) was used for the polar material, and a polypropylene sheet (Nippon Testpanel Co., Ltd.) was used for the polyolefin resin substrate. , Ltd., PP, thickness × width × length = 1.6 × 25 × 100mm). The thickness of the hot-melt adhesives obtained in Examples 1 to 11 and Comparative Examples 1 to 3 was adjusted to 50 μm by thermocompression bonding, and was laminated on a polar material. Then, the polyolefin resin substrate was superimposed on the surface of the adhesive, and a laminate (polar material/adhesive layer/polypropylene resin substrate). The adhesive strength of the above-mentioned laminate was measured by a tensile shear test.

(拉伸剪切試驗(PP/AL拉伸剪切強度)) 依循JIS K 6850(1999)黏著劑之拉伸剪切強度試驗法，使用ORIENTEC CORPORATION製之TENSILON(註冊商標)RTM-100，在25℃環境下，以5mm/分鐘測定剪切強度。極性材料/聚烯烴樹脂基材之間之拉伸剪切強度(MPa)定義為3次之試驗值的平均值。結果表示於表1。 ＜評價基準＞ ○(實際使用上優良):7MPa以上 △(可用於實際使用):5MPa以上 ×(無法實際使用):未達5MPa(Tensile shear test (PP/AL tensile shear strength)) According to JIS K 6850 (1999) Tensile shear strength test method for adhesives, using TENSILON (registered trademark) RTM-100 manufactured by ORIENTEC CORPORATION, in The shear strength was measured at 5 mm/min in a 25°C environment. The tensile shear strength (MPa) between the polar material/polyolefin resin substrate is defined as the average value of the three test values. The results are shown in Table 1. <Evaluation criteria> ○ (excellent in actual use): 7MPa or more △ (can be used in practice): 5MPa or more × (cannot be used in practice): less than 5MPa

(造粒之評價) 將從15mmφ二軸擠製機(TECHNOVEL公司製，KZW15TW)擠製排出之熱熔黏著劑藉由股線切割方式(strand cutting method)丸粒製造裝置進行造粒。結果表示於表1。 ＜評價基準＞ ◎(生產性良好):可連續運轉8小時以上來進行股線切割 ○(可進行生產):可連續運轉4小時以上未達8小時來進行股線切割 △(生產困難):可進行股線切割但連續運轉未達4小時 ×(無法生產):無法進行股線切割(Evaluation of granulation) The hot-melt adhesive extruded and discharged from a 15 mmφ biaxial extruder (manufactured by TECHNOVEL, KZW15TW) was granulated by a strand cutting method pellet manufacturing apparatus. The results are shown in Table 1. <Evaluation Criteria> ◎ (good productivity): Continuous operation for more than 8 hours for strand cutting ○ (production possible): Continuous operation for more than 4 hours but less than 8 hours for strand cutting △ (production difficult): Strand cutting is possible but continuous operation is less than 4 hours × (unable to produce): strand cutting cannot be performed

【表1】

Figure 02_image001
[產業上利用性]【Table 1】
Figure 02_image001
[industrial applicability]

本發明之黏著劑組成物及熱熔黏著劑具有與烯烴系樹脂基材及極性材料之良好的黏著性，可不使烯烴系樹脂基材損傷而進行低溫熱封。The adhesive composition and the hot-melt adhesive of the present invention have good adhesion to the olefin-based resin substrate and polar materials, and can be heat-sealed at low temperature without damaging the olefin-based resin substrate.

無none

Claims (3)

一種黏著劑組成物，含有酸改性聚丙烯(A)、未官能化聚丙烯(B)及聚乙烯(C)，熔點為70~140℃；酸改性聚丙烯(A)的熔點為65℃以上130℃以下；未官能化聚丙烯(B)的熔點為70℃以上135℃以下；相對於酸改性聚丙烯(A)100質量份，含有未官能化聚丙烯(B)140~1500質量份、及聚乙烯(C)10~600質量份。 An adhesive composition, comprising acid-modified polypropylene (A), unfunctionalized polypropylene (B) and polyethylene (C), with a melting point of 70-140° C.; acid-modified polypropylene (A) with a melting point of 65° C. ℃ or more and 130 ℃ or less; the melting point of the unfunctionalized polypropylene (B) is 70 ℃ or more and 135 ℃ or less; relative to 100 parts by mass of the acid-modified polypropylene (A), the unfunctionalized polypropylene (B) contains 140-1500 parts by mass, and 10 to 600 parts by mass of polyethylene (C). 一種熱熔黏著劑，含有如申請專利範圍第1項之黏著劑組成物。 A hot melt adhesive comprising the adhesive composition as claimed in item 1 of the patent application scope. 一種聚烯烴樹脂基材與極性材料之疊層體，係藉由如申請專利範圍第2項之熱熔黏著劑進行黏著而成。A laminated body of a polyolefin resin base material and a polar material is formed by adhering the hot-melt adhesive as claimed in item 2 of the patent application scope.
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